Sorption Enhancement Research Articles

Sorption of curium by silica colloids: Effect of humic acid

Sorption of curium by silica colloids has been studied as a function of pH and ionic strength using 244Cm as a tracer. The sorption was found to increase with increasing pH and reach a saturation value of ∼95% at pH beyond 5.3. The effect of humic acid on the sorption of 244Cm onto silica was studied by changing the order of addition of the metal ion and humic acid. In general, in the presence of humic acid (2mg/L), the sorption increased at lower pH (<5) while it decreased in the pH range 6.5–8 and above pH 8, the sorption was found to increase again. As curium forms strong complex with humic acid, its presence results in the enhancement of curium sorption at lower pH. At higher pH the humic acid present in the solution competes with the surface sites for curium thus decreasing the sorption. The decrease in the Cm sorption in presence of humic acid was found to be less when humic acid was added after the addition of curium. Linear additive model qualitatively reproduced the profile of the Cm(III) sorption by silica in presence of humic acid at least in the lower pH region, however it failed to yield quantitative agreement with the experimental results. The results of the present study evidenced the incorporation of Cm into the silica matrix.

Influence of soil properties on heavy metal sequestration by biochar amendment: 1. Copper sorption isotherms and the release of cations

The amendment of carbonaceous materials such as biochars and activated carbons is a promising in situ remediation strategy for both organic and inorganic contaminants in soils and sediments. Mechanistic understandings in sorption of heavy metals on amended soil are necessary for appropriate selection and application of carbonaceous materials for heavy metal sequestration in specific soil types. In this study, copper sorption isotherms were obtained for soils having distinct characteristics: clay-rich, alkaline San Joaquin soil with significant heavy metal sorption capacity, and eroded, acidic Norfolk sandy loam soil having low capacity to retain copper. The amendment of acidic pecan shell-derived activated carbon and basic broiler litter biochar lead to a greater enhancement of copper sorption in Norfolk soil than in San Joaquin soil. In Norfolk soil, the amendment of acidic activated carbon enhanced copper sorption primarily via cation exchange mechanism, i.e., release of proton, calcium, and aluminum, while acid dissolution of aluminum cannot be ruled out. For San Joaquin soil, enhanced copper retention by biochar amendment likely resulted from the following additional mechanisms: electrostatic interactions between copper and negatively charged soil and biochar surfaces, sorption on mineral (ash) components, complexation of copper by surface functional groups and delocalized π electrons of carbonaceous materials, and precipitation. Influence of biochar on the release of additional elements (e.g., Al, Ca) must be carefully considered when used as a soil amendment to sequester heavy metals.

Enhancement of CO2Sorption Uptake on Hydrotalcite by Impregnation with K2CO3

The awareness of symptoms of global warming and its seriousness urges the development of technologies to reduce greenhouse gas emissions. Carbon dioxide (CO(2)) is a representative greenhouse gas, and numerous methods to capture and storage CO(2) have been considered. Recently, the technology to remove high-temperature CO(2) by sorption has received lots of attention. In this study, hydrotalcite, which has been known to have CO(2) sorption capability at high temperature, was impregnated with K(2)CO(3) to enhance CO(2) sorption uptake, and the mechanism of CO(2) sorption enhancement on K(2)CO(3)-promoted hydrotalcite was investigated. Thermogravimetric analysis was used to measure equilibrium CO(2) sorption uptake and to estimate CO(2) sorption kinetics. The analyses based on N(2) gas physisorption, X-ray diffractometry, Fourier transform infrared spectrometry, Raman spectrometry, transmission electron microscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy were carried out to elucidate the characteristics of sorbents and the mechanism of enhanced CO(2) sorption. The equilibrium CO(2) sorption uptake on hydrotalcite could be increased up to 10 times by impregnation with K(2)CO(3), and there was an optimal amount of K(2)CO(3) for a maximum equilibrium CO(2) sorption uptake. In the K(2)CO(3)-promoted hydrotalcite, K(2)CO(3) was incorporated without changing the structure of hydrotalcite and it was thermally stabilized, resulting in the enhanced equilibrium CO(2) sorption uptake and fast CO(2) sorption kinetics.

Enhancement of chlorophenol sorption on soil by geophagous earthworms ( Metaphire guillelmi)

Earthworms are the dominant soil biomass of many terrestrial ecosystems and markedly influence the physico-chemical and biological properties of soil; however, little is known about the effects of earthworm activities on the environmental behavior of micropollutants in soil. We studied the sorption and desorption of 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol on geophagous earthworm (anecic Metaphire guillelmi) casts of various aging times and on the parent soil. The casts were characteristic of lower pH and higher content of fine particles (silt and clay) than the parent soil. The sorption of the chlorophenols on the soil and casts were well fitted to linear isotherms, with sorption capacity in the order of pentachlorophenol > 2,4-dichlorophenol > 2,4,6-trichlorophenol. The sorption on the cast with different aging time was quite similar and was higher than on the parent soil. The sorption on the soil did not change between pH 7.07 of the soil and pH 6.76 of the casts. The desorption hysteresis of the chlorophenols on the soil and casts was compound specific and 2,4,6-trichlorophenol showed the highest hysteresis. The higher sorption capacity of the casts was not owing to the lowered pH of the casts, but mainly to the higher fine particles in the casts and the possible changes of nature of the soil organic matter through the earthworm gut passage. Our results indicate that geophagous earthworms may change sorption behavior and thus the bioavailability and transport of chlorophenols in soil. Earthworm effects should be considered when evaluating the environmental behavior and risk of organic pollutants in the ecosystems where earthworms are abundant.

Technical and economic study of integrated system of solid oxide fuel cell, palladium membrane reactor, and CO 2 sorption enhancement unit

This paper deals with the integrated system of solid oxide fuel cell (SOFC), palladium membrane reactor (PMR), and CO 2 sorption enhancement (SE) unit. Three configurations of the SOFC systems fed by biogas are considered, i.e., PMR–SOFC, SE–PMR–SOFC, and SE–PMR–SOFC with a retentate gas recycling (SER–PMR–SOFC). The SOFC system equipped with a conventional reformer (CON–SOFC) is considered as a base case. The simulation results show that the capture of CO 2 in biogas before being fed to PMR (SE–PMR–SOFC) can improve H 2 recovery. The performance of SE–PMR–SOFC can be further enhanced by recycling retentate gas from PMR to CO 2 sorption enhancement unit (SER–PMR–SOFC). Compared to CON–SOFC, both SE–PMR–SOFC and SER–PMR–SOFC give higher power density and thus require smaller stack size (the stack size reduction of 1.55% and 8.27% are observed for SE–PMR–SOFC and SER–PMR–SOFC, respectively). The economic analysis is performed to identify the potential benefits of each SOFC configuration. The results indicate that SE–PMR–SOFC and SER–PMR–SOFC are not cost-effective systems compared with CON–SOFC; however, the capture of CO 2 in these SOFC systems offers an environmental benefit. High %total CO 2 capture and low cost of CO 2 capture are achieved under these SOFC systems.

Enhanced soil retention for o-nitroaniline by the addition of a mixture of a cationic surfactant (Cetyl Pyridinium Chloride) and a nonionic surfactant (Polyethylene Glycol Mono-4-nonylphenyl Ether)

The sorption enhancement of o-nitroaniline on a soil by the addition of a mixture of a cationic surfactant (Cetyl Pyridinium Chloride, CPC) and a nonionic surfactant (Polyethylene Glycol Mono-4-nonylphenyl Ether, P0707), as compared with that by individual CPC and P0707, was investigated to examine their potential application in soil retarding for organic contaminants. The maximum sorption coefficients ( K d * ) of o-nitroaniline on modified soils by individual CPC and P0707 were 110 mL g −1 at an added CPC dose of 6000 mg L −1 and 12.5 mL g −1 at an added P0707 dose of 7000 mg L −1, respectively. They were approximately 78 and 8.87 times higher than the sorption coefficients ( K d ) of o-nitroaniline on the un-modified soil (1.41 mL g −1), suggesting that CPC and P0707 can enhance the sorptive capacity of soil for o-nitroaniline. The maximum K d * value of o-nitroaniline on modified soils by the mixture of CPC and P0707 was 144 mg L −1 (at CPC dose of 10,500 mg L −1 and P0707 dose of 6000 mg L −1), which is higher than that on the CPC (or P0707) modified soils and approximately 102 times higher than that on the un-modified soil. Therefore, mixed cationic–nonionic surfactants could be better than individual ones in soil modification to enhance retention of organic contaminants.

Mild pre-heating of organic cation-exchanged clays enhances their interactions with nitrobenzene in aqueous environment

Aqueous sorption kinetics and equilibrium isotherms of nitrobenzene were studied on two series of sorbents that were prepared by (i) replacing inorganic exchangeable cations in Wyoming bentonite with tetraethylammonium (TEA) and benzyltrimethylammonium (BTMA) and (ii) heating synthesized complexes in air at different temperatures (between 150 and 420°C). The aim of this work was to examine recently observed enhancement of aqueous sorption of a probe organic sorbate on organoclays after mild thermal pre-treatment of sorbents. Thermal pre-treatment of TEA- and BTMA-clays at 150°C results in the maximal enhancement of nitrobenzene–sorbent interactions as compared with treatment of original bentonite and its exchange complexes formed with long-chain quaternary ammonium (n-hexadecyltrimethylammonium, HDTMA). Based on C, N content data and FTIR spectra of TEA- and BTMA-clay complexes, no indications of decomposition of organic matter were found in organoclays heated at 250°C (and below this temperature). Suppressed hydration of pre-heated sorbents resulting in a lessening of water–organic sorbate competition for sorption sites is considered to be responsible for thermally induced enhancement of nitrobenzene–sorbent interactions. In the HDTMA-based organoclays, the long-chain aliphatic groups of the quaternary ammonium can additionally interact with clay surface thus competing with organic sorbate–sorbent surface interactions and, in this way, mitigating the enhancement of nitrobenzene sorption on thermally treated sorbents.

Basic and Reactive Dyes Sorption Enhancement of Rice Hull through Chemical Modification

Problem statement: Many studies have been conducted on the removal of either anionic or cationic dyes. However, as a mixture of dyes does commonly exist together in wastewater, therefore it is of great interest to have a material that can remove both types of dyes. Approach: To prepare an inexpensive and efficient sorbent by chemically modifying rice hull for the removal of both basic and reactive dyes. Different chemical modifications were performed on rice hull and a comparison study on the uptake of dyes was carried out. Optimization study was carried out on most promising modified rice hull. Surface morphology of modified rice hull was examined and the functional groups present were determined using FTIR. Results: From the results, it appeared that by using EDA modified rice hull, an appreciable amount of both dyes could be sorbed. Varying the EDA/NRH ratios and heating temperatures affected the uptake of BB3 and RO16. The investigated sorbents were non-porous materials, due to the absence of pores and cavities. Sorption-desorption study showed that a complete recovery of BB3 can be obtained using high concentrations of H2SO4 and HCl but the desorption experiments of RO16 using NH3 and NaOH were not successful. Conclusion: The modification of rice hull with EDA under the optimum conditions (in a ratio of 1.00 g of NRH to 0.02 mole of EDA in a well stirred water bath at 80°C for 2 h) resulted in the formation of a sorbent (MRH) that could be used successfully to remove Both Basic (BB3) and Reactive dyes (RO16).

Enhanced Hydrogen Sorption on Carbon and NiO in the Presence of a Piezoelectric Element

Behaviors of hydrogen sorption on carbon and NiO in the presence of a piezoelectric element were studied. Initiation of this effort was based on the theoretical predictions and experimental evidences that charged species have capabilities to cluster hydrogen molecules. The piezoelectric element is able to autogenously generate charges in hydrogen pressure. Enhanced hydrogen sorption was observed from this study. The observed sorption enhancement supports the assumption that sorbent materials could hold more hydrogen if they are electrically charged. The greater enhancement observed from hydrogen sorption on NiO samples was attributed to the catalysis effect of nickel species, which might split hydrogen molecules into hydrogen atoms and thus make the effect of electric field on hydrogen sorption more effective.

Enhanced hydrogen sorption on carbonaceous sorbents under electric field

The effect of an applied electric field on hydrogen physisorption isotherm on carbonaceous sorbents was studied. Distinctive sorption enhancement was obtained by applying a positive electrical potential of 2000 V to platinum-supported carbon samples. The phenomenon was ascribed to stronger interactions between hydrogen and the sorbent. Theoretical studies suggested that, the interaction between hydrogen and neutral carbon is primarily the electrostatic attraction between the π-bonds of the aromatic rings and the σ-bonds of H 2, which is classified as van der Waals interaction and is weak. However, the interaction between electrically charged carbon and hydrogen might involve orbital interactions between hydrogen and carbon, an interaction stronger than van der Waals attraction. Experimental studies indicated that the presence of platinum would induce dissociation of hydrogen molecules in to hydrogen atoms. The easier accessibility of the atomic orbital might favor the electron transfer from the atomic hydrogen to charged carbon.

Rapid and reversible hydrogen sorption in Mg–Fe–Ti thin films

This study focused on hydrogen sorption properties of 1.5 μm thick Mg–10 at. % Fe–10 Ti, Mg–15 at. % Fe–15 Ti, and Mg–20 at. % Fe–20 Ti films. We show that the alloys display remarkable sorption behavior: At 200 °C the films are capable of absorbing nearly 5 wt % hydrogen in seconds and desorbing in minutes. Furthermore this sorption behavior is stable over cycling. In the Mg–15 at. % Fe–15 Ti alloy there is no kinetic or capacity degradation even after 100 absorption/desorption cycles. Pressure–composition isotherm data for Mg–10 at. % Fe–10 Ti indicates that the sorption enhancement is due to improved kinetics rather than any altered thermodynamics. We envision these alloys as becoming the material of choice for a variety of sensing and storage applications.

Reactivity characteristics of poly(methyl methacrylate) coated nanoscale iron particles for trichloroethylene remediation

The unstable characteristic of nanoscale zerovalent iron (NZVI) has been a drawback in practical application, despite the expectation of an enhanced reactivity. It has been ever-increasing interests to maintain the NZVI stability in air without significant reactivity sacrifice. This study demonstrated a novel method of coating NZVI particles with poly(methyl methacrylate) (PMMA), which protected the core iron nanoparticles from oxidation in air and enhanced their dispersion stability in organic solvents. The reactivity studies on trichloroethene (TCE) reduction showed that the PMMA coated nanoscale zerovalent iron (PNZVI) particles were capable of effectively reducing TCE. The main roles of PMMA on the dechlorination reactions were confirmed to be sorption enhancement, competitive sorption and corrosion inhibition.

The influence of SWCNT–metallic nanoparticle mixtures on the desorption properties of milledMgH2 powders

We have examined the effect of single-walled carbon nanotube(SWCNT)–metallic nanoparticle additions on the hydrogen desorption behavior ofMgH2 after high-energy co-milling. The metallic nanoparticles were the catalysts used for theSWCNT growth. The co-milling consisted of high-energy planetary milling in an inertargon environment of the hydride powder mixed with the SWCNTs. Identically milled pureMgH2 powders were used as a baseline. The composites were tested using a combined differentialscanning calorimeter and thermogravimetric analyzer, while the microstructures wereexamined using a variety of techniques including x-ray diffraction and transmission electronmicroscopy (TEM). We found that the SWCNT–nanoparticle additions do have aninfluence on the desorption kinetics. However, the degree to which they are effectivedepends on the composite’s final state. The optimum microstructure for sorption, obtainedafter 1 h of co-milling, consists of highly defective SWCNTs in intimate contact withmetallic nanoparticles and with the hydride. This microstructure is optimum,presumably because of the dense and uniform coverage of the defective SWCNTs on theMgH2 surface. Prolonged co-milling of 7 h destroys the SWCNT structure and reduces theenhancement. Even after 72 h of co-milling, when the SWCNTs are completelydestroyed, the metallic nanoparticles remain dispersed on the hydride surfaces.This indicates that the metallic nanoparticles alone are not responsible for theenhanced sorption and that there is indeed something catalytically unique about adefective SWCNT–metal combination. Cryo-stage TEM analysis of the hydridepowders revealed that they are nanocrystalline and in some cases multiplytwinned. To our knowledge this is the first study where the structure of milledα-MgH2 has been directly imaged. Since defects are an integral component of hydride-to-metalphase transformations, such analysis sheds new insight regarding the fundamentalmicrostructural origins of the sorption enhancement due to mechanical milling.

Influence of organic amendments on the sorption of pentachlorophenol on soils

The influence of pH on the sorption of pentachlorophenol (PCP) onto three organic amendments, char, humic acid (HA) and peat, and the effect of organic amendments on PCP sorption to three kinds of soils were evaluated. The sorption of PCP on these sorbents fitted the Freundlich model well, suggesting that PCP sorption isotherms were nonlinear with exponential coefficient (N) value lower than 1. The PCP sorption capacity on three organic amendments and the N values increased with decreasing pH. The sorption capacities were in the order: char > HA > peat. Organic amendments resulted in an enhancement of sorption capacities of soils. The N values of PCP sorption on soils were decreased by char amendment and increased by HA and peat amendments. This study demonstrated that application of traditional organic amendments led to the enhancement of PCP sorption by soils. This information may aid both in predicting environmental fates of hydrophobic ionizable organic compounds and in developing remediation strategies for them.

Effect of background electrolytes on the adsorption of nitroaromatic compounds onto bentonite

To further elucidate interaction of nitroaromatic compounds with mineral surface, the sorption of m-dinitrobenzene (m-DNB) and nitrobenzene to original bentonite in aqueous solution containing different electrolytes (i.e., KCl, NH4Cl, CaCl2 and Tetramethylammonium bromide (TMAB)) was studied. The sorption of m-DNB was greatly enhanced with the presence of KCl and NH4Cl, while little influence was observed with CaCl2 and TMAB, following the order of KC1 > NH4Cl >> TMAB, CaCl2, or DI water. For nitrobenzene, sorption enhancement only occurred at high nitrobenzene concentrations in the presence of KCl, and the solute equilibrium concentration at inflexion point was lowered with increasing KCl concentration. These sorption enhancements were significantly promoted with the increase of electrolyte concentration. The salting-out effect is insufficient to account for the sorption enhancement by original bentonite with increasing KCl or NH4Cl concentration. X-ray diffraction patterns of bentonite suspensions indicated that the sorption enhancement of m-DNB was attributed to the intercalation of K+ or NH4+ into bentonite interlayer and then dehydration with m-DNB to form inner-sphere complexes, which caused previously expanded bentonite interlayers to collapse in aqueous suspension, thus further enhanced the interaction of phenyl with siloxane surface. In comparison, the sorption enhancement of NB is attributed to the formation of outer-sphere complexes with K+ at high solute-loadings (> 200-400 mg/kg). The sorption of m-DNB to initially modified TMA(+)-bentonite and K(+)-bentonite was almost the same as respective sorption to original bentonite in solution containing TMA+ and K+.

Copper adsorption on humic acid coated gibbsite: comparison with single sorbent systems

Environmental context. Adsorption processes control the mobility and bioavailability of nutrients and contaminants in soils, sediments and aquatic systems. Natural organic matter and aluminium oxides are important reactive materials present in natural systems and their mutual interaction may alter the surface properties of both materials, playing an important role on the fate of different contaminants, such as copper, in the environment. The present study illustrates the importance of these interactions, showing that the presence of natural organic matter has a synergic effect on the copper adsorption on the aluminium oxide surface. Abstract. Copper adsorption processes on aluminium oxides may significantly control the mobility and transport of copper ions in soils and surface waters. The binding of protons and copper to humic acid (HA) and to gibbsite as single sorbent systems was investigated and the results then used to test the validity of the Linear Additivity Model (LAM) for describing copper binding to gibbsite/HA systems. More copper was adsorbed in the gibbsite/HA/Cu2+ ternary system, at pH 4 and 6 and ionic strength 0.1 M, than in the corresponding binary systems. Although copper adsorption on gibbsite at pH 4 is rather small, the enhancement in sorption was noteworthy, and can be attributed to the formation of ternary complexes and changes in the electrostatic potentials at the mineral surface or at the HA as a result of their mutual interaction. The LAM predicted satisfactorily the experimental results at pH 6, whereas it underestimated the copper binding at pH 4.

Sorption enhancement of 1-naphthol onto a hydrophilic hyper-cross-linked polymer resin

A hydrophilic hyper-cross-linked polymer resin NDA-150 was developed to remove 1-naphthol from the contaminated waters. The sorption performance of 1-naphthol on NDA-150 was explored and compared with that on the commercial hydrophobic resin XAD-4. The sorption rates of 1-naphthol onto both of the two resins obey the pseudo-second-order kinetics, and are limited by the successive steps of film diffusion and intraparticle diffusion. The greater sorption rate on XAD-4 than NDA-150 is probably due to the larger average pore diameter of XAD-4. All the adsorption isotherms can be represented by Langmuir equation. The larger capacity and stronger affinity of NDA-150 than XAD-4 probably result from the abundant microporous structure and polar groups of NDA-150. In aqueous phase hydrophobic XAD-4 adsorbs 1-naphthol driven principally by enthalpy change, while the adsorption onto hydrophilic NDA-150 driven mainly by entropy change. The breakthrough and the total sorption capacity of NDA-150 to 1-naphthol were obtained to be 1.10 and 1.58 mmol mL −1 resin at 293 K, respectively. Nearly 100% regeneration efficiency for the resin was achieved by ethanol at 313 K.

Sorption of phenanthrene by dissolved organic matter and its complex with aluminum oxide nanoparticles

Intent of this study was to explore the potential application of polymerin, the polymeric, dissolved organic matter fraction from olive oil wastewaters, in technologies aimed at remediating hydrophobic organic compounds (HOCs) point-source pollution. Phenanthrene binding with polymerin was investigated. Moreover, the effect of addition of micro and nanoscale aluminum oxides (Al2O3) was studied, as well as sorption of polymerin on the oxides. Phenanthrene binding capacity by polymerin was notably higher than the sorption capacities for both types of Al2O3 particles. Polymerin sorption on nanoparticles was nearly 100 times higher than microparticles. In a three-phase system, using microparticles, higher phenanthrene sorption was found by adding into water polymerin, oxides and phenanthrene simultaneously. In contrast, using nanoparticles, a considerable enhancement of phenanthrene sorption was shown by adding phenanthrene to a pre-formed and dried polymerin-oxide complex. These findings support the application of polymerin, especially associated with Al2O3 nanoparticles, in remediation of water contaminated with HOCs. This work highlights the significant role of nanoparticles.

Effect of sorbed nonylphenol on sorption of phenanthrene onto mineral surface

The effect of sorbed nonylphenol (NP) at low levels on phenanthrene sorption onto the mineral surfaces (organic-removed sediment, kaolinite) and a natural sediment with low organic content was investigated in this study. NP could be sorbed on the sediment and the minerals, and part of sorbed NP interacted with the solid surface stably. At very low concentrations, sorbed NP was observed to inhibit the sorption of phenanthrene on the hydrophilic mineral surfaces (organic-removed sediment and kaolinite) based on the change of phenanthrene apparent solid–liquid distribution coefficients. When the amount of sorbed NP increased to higher levels, enhancement of phenanthrene sorption occurred. Similar result was also obtained in isotherm experiments. On the mineral sorbents contacting with 1.0 mg/L NP solution previously, the K d values were lower compared with those on the sorbents without sorbed NP. On the sorbents with higher levels of sorbed NP (contacting with 10 mg/L NP solution previously), the K d values increased, while the isotherm tended to be more nonlinear. Concentrations of sorbed NP determined its orientation on the surface, which could presumably affect the water film above the sorbents, or contribute more adsorption sites for phenanthrene.

Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation UO22+, sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)2UO2(H2O)n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO2-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)2UO2(H2O)3 which can form on the dominant {101} surface. However, in the presence of CO2, we find an enhancement of UO2 sorption at low pH and attribute this to a (>FeO)CO2UO2 ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)2UO2CO3. The three proposed surface complexes, (>FeOH)2UO2(H2O)3, >FeOCO2UO2, and (>FeOH)2UO2CO3 are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO2–OH–CO3 aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO2 environments at surface loadings of 0.02–2.0wt% U.